Rheological layering

Rheology. Flow properties of latices are important during processing and in many latex appHcations such as dipped goods, paint, inks (qv), and fabric coatings. For dilute, nonionic latices, the relative latex viscosity is a power—law expansion of the particle volume fraction. The terms in the expansion account for flow around the particles and particle—particle interactions. For ionic latices, electrostatic contributions to the flow around the diffuse double layer and enhanced particle—particle interactions must be considered (92). A relative viscosity relationship for concentrated latices was first presented in 1972 (93). A review of empirical relative viscosity models is available (92). In practice, latex viscosity measurements are carried out with rotational viscometers (see Rpleologicalmeasurement). 

The dependence of release force on the flexibility of the release layers is noted in systems other than silicones. Recent work in olefin release shows that release is a strong function of the density or crystallinity of the layer [44], At a density above 0.9 g/cm release for an acrylate PSA is greater than 270 g/cm. However, when the density of PE is dropped to 0.865 g/cm-, the release force of the same adhesive construction drops to 35 g/cm. An investigation of interfacial friction and slip in these systems has not yet been reported, but again the manipulation of release rheology greatly impacts the measured peel force. 

Rheological methods of measuring the interphase thickness have become very popular in science [50, 62-71]. Usually they use the viscosity versus concentration relationships in the form proposed by Einstein for the purpose [62-66], The factor K0 in Einstein s equation typical of particles of a given shape is evaluated from measurements of dispersion of the filler in question in a low-molecular liquid [61, 62], e.g., in transformer oil [61], Then the viscosity of a suspension of the same filler in a polymer melt or solution is determined, the value of Keff is obtained, and the adsorbed layer thickness is calculated by this formula [61,63,64] ... 

Organotitanates form regular adsorbed layers on the filler surfaces. This assures a high degree of dispersibility of the solid particles of the filler, removal of moisture and air from the surfaces, a material improvement of the rheological properties of filled compositions. Also, it is possible to use much greater percentages of cheap... 

The fact that the appearance of a wall slip at sufficiently high shear rates is a property inwardly inherent in filled polymers or an external manifestation of these properties may be discussed, but obviously, the role of this effect during the flow of compositions with a disperse filler is great. The wall slip, beginning in the region of high shear rates, was marked many times as the effect that must be taken into account in the analysis of rheological properties of filled polymer melts [24, 25], and the appearance of a slip is initiated in the entry (transitional) zone of the channel [26]. It is quite possible that in reality not a true wall slip takes place, but the formation of a low-viscosity wall layer depleted of a filler. This is most characteristic for the systems with low-viscosity binders. From the point of view of hydrodynamics, an exact mechanism of motion of a material near the wall is immaterial, since in any case it appears as a wall slip. 

This formula may be useful as a rheological method for determining the thickness of adsorption layer, which is formed as a result of interaction between a dispersion medium and filler, by the results of measuring the t] versus q> dependence. Especially curious phenomena, connected with surface effects, arise when a mixture of fillers of different nature is used according to concentration of an active filler the introduction of the second (inert) filler can either increase or decrease the viscosity of a multicomponent system [35],... 

The concepts of interface rheology are derived from the rheology of three-dimensional phases. Characteristic for the interface rheology is the coupling of the motions of an interface with the flow processes in the bulk close to the interface. Thus, in interface rheology the shear and dilatational stresses of the interface are in equilibrium with the corresponding shear stress in the bulk. An important feature is the compressibility of the adsorption layer of an interface in contrast, the flow elements of the bulk are incompressible. As a result, compression or dilatation of the adsorption layer of a soluble surfactant is associated with desorption and adsorption processes by which the interface tends to reinstate the adsorption equilibrium with the bulk phase. 

Another remarkable feature of thin film rheology to be discussed here is the quantized" property of molecularly thin films. It has been reported [8,24] that measured normal forces between two mica surfaces across molecularly thin films exhibit oscillations between attraction and repulsion with an amplitude in exponential growth and a periodicity approximately equal to the dimension of the confined molecules. Thus, the normal force is quantized, depending on the thickness of the confined films. The quantized property in normal force results from an ordering structure of the confined liquid, known as the layering, that molecules are packed in thin films layer by layer, as revealed by computer simulations (see Fig. 12 in Section 3.4). The quantized property appears also in friction measurements. Friction forces between smooth mica surfaces separated by three layers of the liquid octamethylcyclotetrasiloxane (OMCTS), for example, were measured as a function of time [24]. Results show that friction increased to higher values in a quantized way when the number of layers falls from n = 3 to n = 2 and then to M = 1. 

Unlike traditional textbooks of tribology, in this book we regard boundary lubrication as a limit state of hydrodynamic lubrication when film thickness is down to molecular dimension and independent of the velocity of relative motion. The discussions are based on the existing results, some from literatures but mostly from the authors own work. The topics are mainly focused on the mechanical properties of boundary films, including rheology transitions, molecular ordering, and shear responses. Ordered molecule films, such as L-B films and SAM, are discussed, with emphasis on the frictional performance, energy dissipation and the effects from structural features. Boundary films can be modeled either as a confined substance, or an adsorbed/reacted layer on the... 

The mechanisms of static friction and stick-slip motion, as discussed in the last section, are supposed to be a good description of dry friction. Another case, perhaps more general in engineering practices, to be addressed in this section is lubricated sliding where liquid lubricant, consisting of a few molecule layers, is confined between two solid walls. Both experimental and theoretical studies indicate, as we have discussed in Chapter 5, that there are substantial changes in rheology of the confined lubricant, and the liquid may transit practically to a solid-like state when film thickness becomes molecularly thin [32,33]. 

This mbber is very tacky in nature and contains acrylic group, which makes it polar in nature. Nanocomposites have been prepared based on this elastomer with a wide range of nanohllers. Layered silicates [53-55] have been used for this preparation. Sol-gel method [56,57], in situ polymerization [58], and nanocomposites based on different clays like bentonite [59] and mica [60] have been described. The mechanical, rheological, and morphological behaviors have been investigated thoroughly. 

Flow of the liquid past the electrode is found in electrochemical cells where a liquid electrolyte is agitated with a stirrer or by pumping. The character of liquid flow near a solid wall depends on the flow velocity v, on the characteristic length L of the solid, and on the kinematic viscosity (which is the ratio of the usual rheological viscosity q and the liquid s density p). A convenient criterion is the dimensionless parameter Re = vLN, called the Reynolds number. The flow is laminar when this number is smaller than some critical value (which is about 10 for rough surfaces and about 10 for smooth surfaces) in this case the liquid moves in the form of layers parallel to the surface. At high Reynolds numbers (high flow velocities) the motion becomes turbulent and eddies develop at random in the flow. We shall only be concerned with laminar flow of the liquid. 

To characterize rheological behavior of materials, some basic terms need to be defined. Consider a liquid material that is subjected to a shearing force as illustrated in Fig. 2. The liquid is assumed to consist of a series of parallel layers with the surface area A, the bottom layer being fixed. When a force is applied on the top layer, the top plane moves at a constant velocity, whereas each lower layer moves with a velocity directly proportional to its distance from the stationary bottom layer. The velocity gradient (dv/dr, the difference in velocity, dv, between the top and bottom planes of liquid separated by the distance, dr) is also called the rate of shear, G ... 

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